US3056754A

US3056754A - Vulcanizable composition comprising rubber and a resinous complex reaction product of a phenol-formaldehyde condensate and a metal chloride, and process for vulcanizing same

Info

Publication number: US3056754A
Application number: US834397A
Authority: US
Inventors: Giller Arnold
Original assignee: Chemische Werke Albert
Current assignee: Hoechst AG Werk Kalle Albert
Priority date: 1958-09-03
Filing date: 1959-08-18
Publication date: 1962-10-02
Anticipated expiration: 1979-10-02

Description

3,056,754 Patented Oct. 2, 1962 VULCANIZABLE cor/mosirroN coMrRIsiNG RUBHER AND A RnsiNoUs COMPLEX REAC- TlON rnonnor or A PHENOL-FORMALDE- HYDE CGNDENSATE AND A METAL curio- REDE, AND PRGCESS FUR VULCANIZING SAME Arnold Gilles, Wiesbaden, Germany, assignor to This invention relates to a method of vulcanizing natural and synthetic rubber, using resinous complex compounds formed by alkylphenol resins with metal halides as vulcanizing agents.

Various processes are known whereby natural rubber as Well as synthetic elastomers may be cross-linked or vulcanized by reaction with alkylphenol resins. The term alkylphenol resins is understood to embrace resins obtained by formaldehyde condensation of phenols under alkaline conditions which have a substituent with at least three carbon atoms attached in the orthoor para-position, preferably in the para-position. These vulcanization processes have found only limited application because they were either unsatisfactory in their effect or because they exhibited substantial shortcomings.

For example, it is known that natural rubber or butadiene-acrylonitrile rubber can be vulcanized with alkylphenol resins, and that the vulcanizing effect of these resins can be improved by the addition of metal oxides and/or carbon black. This vulcanization process, however, did not acquire practical importance because despite the use of large quantities of resins even extended vulcanization periods produced vulcanizates with unsatisfactory technological properties.

Further, the vulcanization of synthetic rubber of the GR-S type with smaller amounts of alkylphenol dialcohols has been described. While, according to the patent literature, rubber compositions with satisfactory technical properties could be achieved when vulcanization-promoting substances, such as para-formaldehyde or triethanolamine, were simultaneously used, the vulcanization temperatures and periods required therefor, generally 30 to 60 minutes at 195 Q, Would make it appear to be doubtful whether the vulcanization was actually eifected by the 2,6-dimethylol-4-tertiary-butylphenol additive, because it has recently been found that synthetic rubber of the type employed can also be vulcanized by purely thermal action, that is without any vulcanizing agents as such [see H. Luttrop, Kautschuk und Gummi, 10, WT 30-38 (1957)].

It is further known that trivalent phenols, such as pyrogallol or phloroglucinol, may be used for the vulcanization of styrene-butadiene copolymerizates, and that this vulcanization can be accelerated by adding aromatic amines, such as aniline or oor p-nitroso-dimethylaniline, or small amounts of metal chlorides, such as SnCl FeCl or A1Cl In the special case of vulcanization of mixtures of butyl rubber and carbon black, the use of alkylphenol resins, which are obtained by condensation of phenols having alkyl, aryl or aralkyl groups in para-position with formaldehyde, as vulcanizing agents has led to substantially more favorable results because this vulcaniza' tion process can be considerably improved by the addition of metal halides. However, the preparation of butyl rubber-carbon black mixtures containing alkylphenol resins and metal halides presents considerable difiiculties. Although the alkylphenol resins can be ad mixed very smoothly with elastomers of all types, the metal halides, such as FeCl -6H O or Sn Cl 2H O, melt when they are worked into butyl rubber on mixing rolls and, depending upon the content of water of crystallization, either form an aqueous film on the roll or increase the stickiness of the mixture to a large degree. If an aqueous film is formed, the rolls no longer grip the elastomer mixture and the initially smooth and uniform sheet may tear or completely fall oif the roll. If the elastomer mixture becomes too tacky, it often sticks to the last roll and may then be worked and removed only with tedious effort. An orderly performance of the mixing process is then no longer possible.

Moreover, the free metal halides have a corrosive effect and strongly attack the mixing rolls during the mixing process (see Service Bulletin -4, January 1958, Thiokol Chemical Corp). It has further been found that the physical properties of butyl rubber compositions which have been vulcanized separately with alkylphenol resins and metal halides are to a certain extent dependent upon the mixing procedure used in preparing the mixtures. The sequence and the time intervals in which the phenol resin and the metal halides are incorporated in the mixtures are of some importance.

The use of metal halides free from water of crystallization, such as ZnCl does not offer any advantages, because these substances must first be brought into aqueous solution, so that the same difficulties then result as when the metal halides containing water of crystallization are used.

I have now surprisingly found that rubber compositions, and preferably butadiene-styrene compositions and butyl rubber compositions, that is, rubbery copolymers of conjugated diolefins with monoeth ylenically unsaturated copolymerizable monomers, can be worked into high-quality vulcanizates under conditions customary in the rubber industry if complex resinous products, which are obtained by reaction of alkylphenol resins with metal halides and which are described in greater detail below, are used as vulcanizing agents because the above-men tioned difiiculties do not occur upon working the complex compounds into the rubber.

The resinous vulcanizing agents which are employed in accordance with the present invention are, as such, not the subject matter of the invention. They may, for example, be prepared by reacting alkylphenol resins, which are formed in accordance with known methods by condensation under alkaline conditions of p-alkyl-, parylor p-aralkyl-substitut'ed phenols with formaldehyde, with those metal halides which are capable of forming ansolvo-acids, preferably SnCl '2H O and FeCl -aq, under mild conditions.

While the alkylphenol resins may also be reacted with metal bromides to form complex compounds, those formed with metal chlorides are technically of primary importance.

The reaction products are complex compounds which distinctly dilfer in their properties from simple mechanical mixtures of alkylphenol resins and metal halides. For instance, the complex resin obtained from a p-diisobutyl substituted alkylphenol resin and stannous chloride is, in contrast to a corresponding simple mixture, clear and transparent and forms a clear solution in benzene hydrocarbons and in certain quantities of aliphatic hydrocarbons. Upon reaction of ferrous or ferric chloride with an alkylphenol resin the formation of a complex compound may clearly be recognized. without any further chemical proof, by a deepening of the color of the reaction mixture.

The reaction of the alkylphenol resin with the metal halide may be regarded partially or exclusively as an ester formation between a more or less high-molecular spea /a weight, para-substituted phenol-dialcohol, as described by K. Hultzsh in Chemie der Phenolharze on page 165, and a metal chloride-hydroxoacid, i.e. ansolvo-acid [see Meerwein, Liebigs Annalen der Chemie, 455 (1927), 227 to 253]. Thus, the chlorides of tin, iron, zinc and aluminum are able to form ansolvo-acids. The ansolvoacid esters thus formed are believed to have the following structural formula:

OH an on oH-MeX..)-oH2-Qom-0-oHrOorn-Uomonmom l R R R wherein n is an integer from 1 to 4, inclusive, and preferably 2,

R is an alkyl, aryl or aralkyl group, such as p-tertiary butyl, p-diisobutyl, p-phenyl or p-benzyl,

X is a halogen, preferably chlorine, and

Me is a metal.

The amounts of alkylphenol resins and metal halides which are preferably reacted with each other to form satisfactory vulcanizing agents in accordance with the present invention are about parts by weight alkylphenol resin per about l-10 parts by weight metal halide. The reaction products obtained thereby are, for the sake of convenience and simplicity, hereinafter referred to as reinforced alkylphenol resins. Illustrative examples of their preparation are the following:

RESIN A 206 gm. p-octyl-phenol were dissolved at a temperature of 80 to 90 C. in 400 gm. of a 10% aqueous sodium hydroxide solution. After cooling to 60 C., to gm. of an aqueous 30% formaldehyde solution were added, and the reaction mixture was condensed at 60 to C. until all of the formaldehyde had entered into the addition reaction, which took about 3 to 4 hours. After cooling, the reaction mixture was neutralized with dilute sulfuric acid, and the oily condensation product which separated out was washed with water until free from sulfates. The syrup thus obtained, which was now free from salts and acids, was dehydrated at C. in a vacuum and was then transformed into a solid resin by further heating to C. under atmospheric pressure. gm. of this resin were dissolved in 30 gm. acetone by heating to 50 C., and the solution thus obtained was admixed with a solution of 60 gm. SnCl -2H O in 30 gm. acetone. While thoroughly stirring it, the viscous resin solution was heated for 30 5 minutes at 80 0., whereby the major amount of the acetone solvent evaporated. A caramel-colored, homogeneous resin was obtained, which was freed from adhering acetone by drying it at 40 C. in a forced-air drying chamber.

RESIN B Its production procedure was the same as for Resin A, except that only 40 gm. SnCl -2H O were used.

RESIN C 50 gm. of a p-tertiary butyl-phenol-formaldehyde resin, known under the trade name of Alresen 142R, were dissolved in about 50 ml. alcohol, and the resulting solution was admixed with a solution f 16.7 gm. FeCl -4H O in 50 ml. alcohol. A bluish-violet solution was obtained, from which a bluish-gray resin was isolated by careful evaporation in vacuo.

The reinforced alkylphenol resins, in comparison with normal alkylphenol resins, are marked by a substantially produceable proper-ties. The rate of vulcanization of the reinforced alkylphenol resins is so high that natural and synthetic rubber compositions may be vulcanized therewith under conditions which are usually applied to elastomer compositions modified with sulfur and accelerators, for example 15 to 45 minutes in a press at 143 to 154 C.

The use of the reinforced alkylphenol resins as vulcanizing agents therefore represents a substantial advance over the use of ordinary alkylphenol resins, which vulcanize only very slowly, and over the use of mixtures of alkylphenol resins with metal halides because their incorporation into elastomers is connected with considerable difficulties.

In the vulcanization of natural and synthetic rubber with reinforced alkylphenol resins the concurrent use of other additives which accelerate the vulcanization is not necessary as such. However, if special vulcanizing effects are desired, it is readily possible to modify the compositions additionally with metal halides, alkylphenol resins or metal oxides.

The quantity of reinforced alkylphenol resins necessary for vulcanization depends upon the type of rubber and upon .the composition of the reinforced alkylphenol resin. In general, however, at least 3 parts by weight reinforced alkylphenol resin per 100 parts by weight rubber are required. Most advantageous are 8 to 20 parts reinforced alkylphenol resin per 100 parts rubber. Still larger amounts may also be used.

The suitability of the reinforced alkylphenol resin for the vulcanization of natural and synthetic rubber is completely surprising. To begin with, it could not have been expected that metal halides which are capable of forming ansolvo-acids would react with alkylphenol resins to form stable complex compounds, because it is well known that,

due to their acid character, the ansolvo-acids have a con-.

densing effect on resols and considerably accelerate the transformation of resols into resinates even in small quantities. Furthermore, it could reasonably have been expected that if the alkylphenol resols formed a complex 0 with a metal halide the terminal methylol groups of the O goods and the like, as illustrated by the following examples. The quantities of ingredients are given in parts by weight.

Example I Vulcanizable synthetic rubber Compositions I and II 75 were compounded from the following ingredients:

Composi- Composivulcanization temperature 143 C. 150 C.

tion I, tion II, parts parts l Vulcanization time (minutes)... 15 30 45 15 30 45 Tensile strength (kg/cm?) 140 148 143 150 146 144 Butadiene-styrcne synthetic rubber copoly- Ultimate elongation (percent) 474 461 438 466 423 386 merizate Pliofiex 1500 (for specifications Modulus at 150% elongation see Products, Profits and Ilioflex, April (kg/cm!) 29 31 33 33 33 35 1958, published by Goodyear Tiroand Rub- Modulus at 300% elongation her Company, Akron, Ohio) 100. 0 100.0 (kg/cm.) 2 78 S6 90 86 92 101 Stearic acid 1.0 1.0 Tear-resistance by slit test 50.0 50.0 kg./cm, 27 2s 24 25 25 21 2.0 2.0 Hardness Shore A (degrees) r 61 63 64 62 64 65 12.0 15.0 Rebound elasticity (percent)-.. 6 6 6 6 6 6 The synthetic rubber polymerizate was placed on mixing Thus, Composition III produced a high-quality vulcanirolls, and when a continuous sheet was formed the mineral zate after vulcanization for only minutes at 143 C. oil, the resin and the stearic acid were consecutively added 15 and worked in. Thereafter, the carbon black was added, Example 111 the batch was homogenized by periodically cutting the sheet on the roll to bring fresh material through the bite. 1 52 2 ggii g g f lgz gffigf gg f gghg and VI The following table shows the physical characteristics of p a g the vulcanized synthetic rubber compositions after vary- C C c o omposioniposiotuposimg periods of vulcanization at a temperature of 154 C. tion Iv, tion V, tion VI,

parts parts parts Composition I Composition 11 113515361 r ltjibberlfinjlaiy 365 i 4 e Vuleanimtlon Temperature 154 C 154 C flgg jf fiesin 1g.-- vulcanization time (minutes)--. 15 i5 30 45 em Tensile strength (kg. cm. S 213 Ultimate elongation percent 527 Modulus at 150% elongation 35 39 43 57 68 74 The compositions were compounded by the procedure (kg/0111. 30 described in Example II. Resins B and C were as easy to 101 109 123 158 185 190 work into the rubber as Resin A. The compositions did Tear-resurgence y slit test 8 23 23 24 23 22 not stick to the rolls and no corrosion was observed. The n riiii'staizi'iiiiiatiij:11: Z2 5.. 64 59 70 follpwing table shows the ys properties 01 e v l- Reboun e astic y (p t).-- 35 35 36 35 35 85 canized butyl rubber compositions after vulcanization at 150 C. for varying periods of time.

Composition IV Composition V Composition VI Vulcanization temperature... 150 C. 150 0. 150 C.

vulcanization time (minutes)- 15 30 45 15 30 45 15 30 45 Tensile strength (kg./cm. 94 111 121 155 134 135 121 116 125 Ultimate elongation (percent) 594 540 532 530 477 434 739 668 662 Modulus at 150 percent elongation (kg./cm. 18 23 24 25 29 31 19 15 19 Modulus at 300 perce t el gation (kg/cm?) 41 51 69 66 77 83 35 38 42 Tear-resistance by slit test (kg/cm!) 20 21 23 24 24 20 2s 23 24 Hardness Shore A (degrees) 56 59 61 62 60 63 64 Rebound elasticity (percent).. 6 6 6 6 6 6 6 6 6 Example II Example IV A vulcanizable butyl rubber Composition III was compounded -from the following ingredients:

Parts Butyl rubber Enjay 365 (for specifications see Enjay Butyl, published by Enjay Company,

Inc., New York, New York) 100.0 MPC carbon black 60.0 Stearic acid 1.0 Resin A 8.0

Vulcanizable butyl rubber Compositions VII and VIII with light-colored reinforcing fillers instead of carbon black were compounded from the following ingredients:

Composi- Composition VII, tion VIII, parts parts Butyl rubber Elijay 365 100. (l 100. 0 Ultrasil VN 3 (pure precipitated silicic acid). 50.0 50.0 Stearic acid 1. 0 1. 0 Resin A 10.0 12.0

The butyl rubber was placed on a cold mixing roll and was milled until a smooth sheet was formed. Thereafter, the stearic acid, half of the Ultrasil VN 3 filler, the resin and the remaining amount of filler were worked in consecutively. Finally, the sheet was homogenized by cutting it several times on the roll and, rolling it again each time. No diiiiculties were encountered in compounding these vulcanizable compositions. The following table shows the physical properties of the vulcanized butyl rubber Composition VII Composition VIII vulcanization Temperature 150 0. 150 C.

vulcanization time (minutes)... 30 45 15 30 45 Tensile strength (kg/cm?) 113 138 141 142 152 148 Ultimate elongation (pcrcent). 882 808 736 831 752 712 Modulus at 150% elongation (kg/cm?) 17 17 19 17 19 19 Modulus at 300% elongation (kg/cm!) 27 33 40 31 40 42 Tear-resistance by slit test (kg cm?) 27 27 25 32 28 33 Hardness, Shore A (degrees) 56 59 60 55 l6 (l1 Rebound Elasticity (percent) 6 8 8 7 8 8 Example V A vulcanizable natural rubber Composition IX was compounded from the following ingredients:

Parts Smoked sheets 100.0 Carbon black 50.0 Stearic acid 1.0 Mineral oil 2.0 Resin A 15.0

The ingredients were compounded as described in Example I. The following table shows the physical properties of vulcanized natural rubber Composition IX after vulcanization at 154 C. for varying periods of time.

vulcanization temperature vulcanization time Tensile Strength (kg/cm. Ultimate elongation (percent) Modulus at 150% elongation (kg/cm!) Hardness, Shore A (degrees) Rebound elasticity (a percent) Thus, vulcanizates of natural rubber having good hardness, elasticity modulus and elongation characteristics were also obtained with the aid of the reinforced alkylphenol resins according to the invention as vulcanizing agents.

Example VI A vulcanizable butadiene-acrylonitrile rubber Composition X was compounded from the following ingredients:

The butadiene-acrylonitrile copolymerisate was placed on a mixing roll and allowed to form a smooth sheet. Thereafter, a half of the carbon black, the stearic acid, the Naftolen, the plasticizer, the Resin A and the remaining amount of carbon black were consecutively worked in. The following table shows the physical properties of the vulcanized butadiene-acrylonitrile rubber Composition X 8 after vulcanization at 143 and 154 C. for varying period of time:

Vulcanization temperature 143 0. 154 C.

vulcanization time (minutes). 15 30 45 15 30 45 Tensile strength (kg./cm. 136 144 127 151 Ultimate elongation (percent) 850 776 710 747 732 721 Modulus at 300% elongation (kg/cm?) 27 31 35 31 38 40 Modulus at 500% elongation (kg/cm?) 60 71 79 69 83 88 Tear-resistance by slit test (kg/cm?) 26 25 24 25 28 24 Hardness, Shore A (degrees) 46 47 48 47 48 49 Rebound elasticity (percent)- 10 10 10 10 10 10 While the present invention has been illustrated with the aid of specific examples, it will be readily apparent to those skilled in the art that the invention is not limited to these examples and that various changes and modifications may be made without departing from the spirit of the invention or the scope of the appended claims.

I claim:

1. In a process of vulcanizing elastomer compositions of rubbers selected from the group consisting of natural rubber and rubbery copolymers of conjugated diolefins with monoethylenically unsaturated copolymerizable monomers, the improvement which comprises incorporating into said elastomer compositions as a sole vulcanizing agent a resinous complex reaction product formed from (1) a condensation product of formaldehyde with a phenol substituted by a hydrocarbon radical selected from the group consisting of alkyl, aryl and aralkyl, and (2) an ansolvo-acid-forming metal chloride selected from the group consisting of the chlorides of tin, iron, zinc and aluminum.

2. In a process of vulcanizing elastomer compositions of rubbers selected from the group consisting of natural rubber and rubbery copolymers of conjugated diolefins with monoethylenically unsaturated copolymerizable monomers, the improvement which comprises incorporating into said elastomer compositions as a sole vulcanizing agent a resinous complex reaction product formed from (1) about 10 parts by weight of a condensation product of formaldehyde with a phenol substituted by a hydrocarbon radical selected from the group consisting of alkyl, aryl and aralkyl, and (2) about 1 to 10 parts by weight of an ansolvo-acid-forming metal chloride selected from the group consisting of the chlorides of tin, iron, zinc and aluminum.

3. In a process of vulcanizing elastomer compositions of rubbers selected from the group consisting of natural rubber and rubbery copolymers of conjugated diolefins with monoethylenically unsaturated copolymerizable monomers, the improvement which comprises incorporating into said elastomer compositions as a sole vulcanizing agent a resinous complex reaction product formed by about (1) 10 parts by weight of a condensation product of formaldehyde with a phenol substituted by a hydrocarbon radical selected from the group consisting of alkyl, aryl and aralkyl, and (2) about 1 to 10 parts by weight of a tin chloride.

4. In a process of vulcanizing elastomer compositions of rubbers selected from the group consisting of natural rubber and rubbery copolymers of conjugated diolefins with monoethylenically unsaturated copolymerizable monomers, the improvement which comprises incorporating into said elastomer compositions as a sole vulcanizing agent a resinous complex reaction product formed by about (1) 10 parts by weight of a condensation product of formaldehyde with a phenol substituted by a hydrocarbon radical selected from the group consisting of alkyl, aryl and aralkyl, and (2) about 1 to 10 parts by Weight of an iron chloride.

5. A vuloanizable elastomer composition consisting essentially of a rubber base material selected from the group consisting of natural rubber and rubbery copolymers of conjugated diolefins with monoethylenically unsaturated copolymerizable monomers, a filler, a plasticizer, and as a sole vulcanizing agent a resinous complex reaction product formed from (1) a condensation product of formaldehyde with a phenol substituted by a hydrocarbon radical selected from the group consisting of alkyl, aryl and aralltyl, and (2) an ansolvo-acid-forming metal chloride, selected from the group consisting of the chlorides of tin, iron, zinc and aluminum.

6. A vulcanizable elastomer composition consisting essentially of a rubber base material selected from the group consisting of natural rubber and rubbery copolymers of conjugated diolefins with monoethylenically unsaturated copolymerizable monomers, a filler, a plasticizer, and as a sole vulcanizing agent a resinous complex reaction product formed by about (1) parts by weight of a condensation product of formaldehyde with a phenol substituted by a hydrocarbon radical selected from the group consisting of alkyl, aryl and aralkyl, and (2) about 1 to 10 parts by weight of a metal chloride capable of forming an ansolvo-acid selected from the group consisting of the chlorides of tin, iron, zinc and aluminum, the weight ratio of vulcanizing agent to rubber base material being 1 to 10 parts of vulcanizing agent to 100 parts rubber base material.

7. A vulcanizable elastomer composition consisting essentially of a rubber base material selected from the group consisting of natural rubber and rubbery copolymers of conjugated diolefins with monoethylenically unsaturated copolymerizable monomers, a filler, a plasticizer, and as a sole vulcanizing agent a resinous complex reaction product formed by about 1) 10 parts by Weight of a condensation product of formaldehyde with a phenol substituted by a hydrocarbon radical selected from the group consisting of alkyl, aryl and aralkyl, and (2) about 1 to 10 parts by Weight of a tin chloride, the weight ratio of vulcanizing agent to rubber base material being 1 to 10 parts of vulcanizing agent to parts of rubber base material.

8. A vulcanizable elastomer composition consisting essentially of a rubber base material selected from the group consisting of natural rubber and rubbery copolymers of conjugated diolefins with monoethylenically unsaturated copolymerizable monomers, a filler, a plasticizer, and as a sole vulcanizing agent a resinous complex reaction product formed by about (1) 10 parts by weight of a condensation product of formaldehyde with a phenol substituted by a hydrocarbon radical selected from the group consisting of alkyl, aryl and aralkyl, and (2) about 1 to 10 parts by weight of an iron chloride, the weight ratio of vulcanizing agent to rubber base material being 1 to 10 parts of vulcanizing agent to 100 parts of rubber base material.

References Cited in the file of this patent UNITED STATES PATENTS 1,150,642 Stockhausen et al. Aug. 17, 1915 2,434,129 Throdahl Jan. 6, 1948 2,726,224 Peterson et a1 Dec. 6, 1955 FOREIGN PATENTS 790,803 Great Britain Feb. 19, 1958

Claims

1. IN A PROCES OF VULCANIZING ELASTOMER COMPOSITION OF RUBBERS SELECTED FROM THE GROUP CONSISTING OF NATURAL RUBBER AND RUBBERY COPOLYMERS OF CONJUGATED DIOLEFINS WITH MONOETHYLENICALLY UNSATURATED COPOLYMERIZABLE MONOMERS, THE IMPROVEMENT WHICH COMPRISES INCORPORATING INTO SAID ELASTOMER COMPOSITIONS AS A SOLE VULCANIZING AGENT A RESINOUS COMPLEX REACTION PRODUCT FORMED FROM (1) A CONDENSATION PRODUCT OF FORMALDEHYDE WITH A PHENOL SUBSTITUTED BY A HYDROCARBON RADICAL SELECTED FROM THE GROUP CONSISTING OF ALKYL, ARYL AND ARALKYL, AND (2) AN ANSOLVO-ACID-FORMING METAL CHLORIDE SELECTED FROM THE GROUP CONSISTING OF THE CHLORIDES OF TIN, IRON, ZINC AND ALUMINUM.